Process for printing with dye



Patented Aug. 3, 1954 PROCESS FOR PRINTING WITH DYE-.

STUFFS OF SUBSTANTIVE CHARAC- TER AND PRINTING PREPARATION THEREFOR Jacques Wegmann and Karl Menzi, Basel, Switzerland, assignors to Ciba Limited, Basel, Switzerland, a Swiss firm No Drawing. Application September 5, 1950, Serial No. 183,284

Claims priority, application Switzerland September 19, 1949 14 Claims. (01. 8-62) This invention relates to a process for printing with dyestuffs of substantive character, viz. dyestufis possessing an afiinity for cellulosic fibers. As used herein, the term cellulosic fibers comprises the fibers containing native or regenerated cellulose; it does not comprise fibers from cellulose esters such as cellulose acetate.

The invention is based on the observation that valuable prints can be produced when a printing preparation is employed which contains a metal complex compound which is difiicultly soluble per se, of a substantive dyestuff, together with an organic nitrogen base which corresponds to the general formula in which R1 indicates a hydrogen atom, an alkyl group with at most three carbon atoms or a hydroxymethyl group, R2 a hydrogen atom or a methyl group and n a whole number which is at most 4 but advantageously 2.

The difiicultly soluble metal complex compounds of substantive dyestuffs which are suitable for the present process may contain as complex combined metal for example chromium or iron but especially a metal of an atomic number ranging from 27 to 29, viz. nickel, cobalt or preferably copper. The metal-free dyestuffs from which they are derived are to be substantive and therefore contain one or more of the known substantive groupings. As such may be mentioned the acid amide, especially urea, group, the 1:3:5-triazine grouping, the para-diamine structure, the benzidine radical, the radical of 2-amino-5-hydroxynaphthalene-7-sulfonic acid or of an N- substitution product thereof and so on. In order that the metal complex compounds produced The metal complex compounds employed for" the present process may for example be of the type of the ortho:ortho-dihydroxyazo-metal complexes or of the type of the ortho-hydroxyortho-carboxy-azo-metal complexes. In addition there are also individual dyestuffs of which the metal complexes are based upon thesalicylic acid grouping and salicylic acid groupings may also take part in the complex formation in addition to the other groupings set forth above.

A number of very valuable dyestuffs which are suitable for the present process are obtained from tetrazotized 3:3 dihydroxy 4:4 diaminodiphenyl and also from tetrazotized 4:4'-diaminocliphenyl-3:3-dicarboxylic acid or -3:3-di-(hydroxyacetic acid) and coupling components which couple in ortho-position to a hydroxyl group, as for example l-hydroxynaphthalenes which couple in 2-position, 2-hydroxynaphthalenes and pyrazolones. Such dyestuffs may also be produced by coupling of ortho-hydroxyor ortho-carboxydiazo compounds of the benzene series with components of marked substantive character, such as N-derivatives of 2-amino-5-hydroxynaphthalene- 7-sulfonic acid of good substantivity, or pyrazolones, especially dipyrazolones, which contain substantive groupings, as for example one or more diphenyl groupings.

The printing preparations to be employed for the present process may contain, as bases which correspond to the formula initially specified, for example those of the following constitution:

CH3 CH3 Ho-oH -cNH-cm M. P. 154-157 C.

The metal complex compounds'of. substantive dyestuffs specified for incorporation into the.

printing preparation may if desired b produced in substance. In many cases it is however possible to produce them immediately before the production of the printing preparations, from the corresponding metal-free dyestufis and suitable metal compounds. In this case it is advantageous to produce the metal complexes under such conditions that a stronglyv acidrreaction or the medium is avoided, for example by the application of sodium metal tartrates as agents providing metal. proceed in such a manner that a metal-free dyestuff is dissolved in relatively little water and .10. It is possible for example to brought to the boil with a mixture' of the. nitrogen:

base to be used, for example 1:2-di-(B-hydroxyethylamino) -ethane, and sodium copper tartrate.-

A solution thus obtained can thereupon bestirred immediately into the thickening to be used in the printing. A metal compound of such a: dye stuli", produced in substance, can be brought to the boil directly with thew-nitrogen base to bebe used with the same result even after prolonged standing.

After printing of'the preparation on'cotton or regenerated cellulose the goods are dried, steamed for 10 minutes and thoroughly rinsed with coldwater; in which operation it is advantageous to 1 add to the final rinsing bath 2 grams per liter of a condensation product from dicyan-diamidin'exand formaldehyde. The goods can be soaped. at 60 C. although this process of development-of the color shade is not necessary. Y

A pure blue print is obtained of excellent fastnessalto-light' and Washing and of a strength which corresponds at least to that which is obtained. when,- according to the known process, the uncoppered dyestufi is used for printing and, after steaming, is coppered in an after-treat inent bath."

If instead of the above specified dyestuif 0.5 part is takenof the'dyestufif from 1- molof 41.4 diamino-diphenyL-Ba3-dicarhoxylicacid and 2 mols of -.'1-(6-sulfo-2'-naphthyl)-3-methyl-5 pyrazolone and the process is otherwise con ducted astdescribed -above,- an orange print is obtainedliirewise ofgood:fastness properties.

Example *2 I 0.5 part of the dyestufi from 1 mol of tetrazotized- 3 :3 -dihydroxy-4 4' -dian1inodiphehyl and 2 mols of 2-B-hydroxyethylamino-5hydroxy-- naphthalenefl-slixlfonic acid of the formula process in general veryfast prints'on cellulosic fibers which as regards strength are surprisingly in no way inferior tothose which are obtained by printing with the corresponding metal-free dyestuils and after-metallization of the dyestuiis on the fiber. The printing process is extremely simple and easy to carry out. 7

The following examples illustrate the invention the parts and percentages being by weight:

Example 1 0.5 part or the alkaline-coupling dyestufi from 1 mol of tetrazotized 3:3' -dihydroxy-4wF-diaminodiphenyl and :2 mols of 2-amino-5-hydroxynaphthalene-7-sulfonicacid is mixed with parts of urea and the wholecovered with 66 parts of hot Water. After addition of 4 parts of 1:2-di-(fi-hydroxyethylamino) -ethane and 10 parts of a 10 per centsolution of sodium oopper tartrate; the mixture-is brought to the boil whereby the: dyestuif dissolves. The solution produced is stirred into 106* parts of neutralized tragacanth thickening (/1000). The printing preparation obtained can be used immedi-' ately on cooling; it is however stable and can OH H0 is mixed with 30 parts of urea and covered with 60 parts of liotwaters- After addition of 4 parts of 1:2-di-'(fihydroxy ethylamino) -ethane and 10 parts of a 10 per cent. solution of sodium copper tartrate, the solution is brought tothe' boil and: stirred into parts of-neutralizeditragacanthi thickening (GO/1000'); Thexprinting' color obtained is stableandyields on cotton after print ing, drying, -steaming for "1G minutes; and: thor--' ough rinsing a pure, greenish blue shade ofteX- cellent fastness to rlight'and washing.

7 Example 3' 1 part of the nickel compound of the dyestufi from 1 mol of tetrazotized 3:3'-dihydroxy4:4'- diaminodiphenyl and 2 molsof Z-c-hydroxyethyl amino-8-hydroxynaphthalene 6-sulfonic acid is mixed with 20'parts of urea "and covered with 55,

parts of Water... After addition" of 4 parts of"- 1:2-di- (;3 hydroxyethylamino)-ethane the solution is brought to".the boil and stirred int0120. parts ,of neutralized tragacanth thickening Printing is carried out, followed by drying,

steaming. for 10 n1inutes in'the Mather-Platt or j in the. starsteamer and thorough rin'sing in 'cold water. 7

The print obtained is a bluish-grey of excellent. fastness to light and washing,

Instead .of the above-mentioned nickel compound the cobalt compound of the same .dyestufi, can be used; a similar color shade'loeing obtained which is likewise of good-fastness to light and Washing.

Example: 4

1 part of thecopper compound of the. dyestuff-.- from-i mol of tetrazotizedfi:3-dihydroxy-4:4'e 1 diaminodiphenyl and 2. mols-of2-fl-hydroxyethyh 6' amino-S-hydroxynaphthalene-7-sulfonic acid is A pure vivid violet is obtained of good fastness m x d wi 30 par s of urea, v d w t 65 parts to washing and excellent fastness to light. of hot water and after the addition of 4 parts of 1 :2-di- ((i-hydroxyethylamino) -ethane dissolved by bringing to the boil. The solution produced 5 is stirred into 100 parts of neutralized tragacanth thickening (60/1000).

Example 6 1 part of the copper compound of the dyestufi from 1 mol of 3:3'-dihydroxy-4:4'-diaminodi- Prmtm is carried out, followed b clr in and steaming :tor 10 minutes in the Ma her Plftt or phenyl and 2 mols of f 1 in the star steamer and thorough rinsing in cold 10 methyl5'pymzolone 1s mlxed Wlth parts of water being advantageous to add the final urea and Covered parts of hot Water. Afrinsing bath 2 grams per liter of a condensation 1561 addition of 4 parts of fiy product from dicyandiamidine and formaldehyde. ethylamino)-ethane the solution is brought to The greenish-blue print Obtained s c fi y the boil and stirred into 120 parts of neutralized fixed and withstands, without bleeding out, a 'tragacanth thickening (60/10.00)

treatment for 10 minutes in a boiling soap bath With this printing color there are produced (5 grams of soap and 2 grams of anhydrous sodl on cotton and viscose Bordeaux red shades of fi ggfig i f g $23 33, Water) the fastness good fastness to light and washing by the opera- By using 1 part of the copper compound of 20 tion of printing, drying, steaming for 10 minutes the dyestuff f 1 mcl of tetrazofized 3;3 and rinsing for 15 minutes in the cold with the hydroxy-:4-diaminodiphenyl and 2 mols of 2- addition of 2 grams per liter of the condensation amino-5-hydroxynaphthalene-'Z-sulfonic acid inproduct from dicyandiamldine and formaldehyde stead of the dyestufi above specified, a somewhat t the last rinsing bath. more reddish blue likewise of good fastness prop- By using instead f the above pecified dyestuff erties is Obtained- 1 part of the copper compound of the d t if yes u In the case of both dyestuffs 1t is not possible from 1 mol of tetrazotized to select the printing thickening without discrimination, since for example with British gum dlamlnodlphenyl and 1 mol of 2-hydroxynaphu thickening, probably owing to reduction phenomthalene on the one d and 1 mol of 2-amino7- ena, considerably redder prints are obtained and hydroXynaphthalene-7-Su1fomc acld on the other on regenerated fibers the dyestuif is to some exand p c di th w s as a v d sc bed, tent destro ed The above des ribed printing there is obtained a powerful blue likewise of excolor however yields both on natural and also on cellent fastness to light and washing. regenerated fibers an unobjectionable result.

Encample 7 Example 5 1 part of the copper compound of the dyestufi 1 part of the copper compound of the dyestuff from 1 mol of-tetrazotized 4:4-diaminodiphenylof the formula GOOH is mixed with 20 parts of urea, 4 parts of 1:2-di- (fi-hydroxyethylamino) -ethane are added and the whole is covered with parts of hot water. After bringing to the boil the solution is stirred into 120 parts of neutralized tragacanth thickening (/1000).

3:3'-dicarboxylic acid and 1 mol of 'l-hydroxynaphthalene-5-sulfonic acid on the one hand and 1 mol of 2-phenylamino-5-hydroxynaphthalene- 7-sulfonic acid on the other, is mixed with 20 parts of urea and covered with 55 parts of hot 55 water. After addition of 4 parts or" 1:2-di-(B-hydroXyethylamino)-ethane, solution is brought about by bringing to the boil and is then stirred Wlth thls Prmtmg color thfare 1s d on into parts of neutralized tragacanth thick cotton and viscose after the prmt has been dried, enjng (60 i GO steamed for 10 minutes and thoroughly rinsed,

Printing is carried out followed by drying, an ex e t y fixed po -Y wsteaming for 10 minutes in the Mather-Flatt or If instead of the above-mentio ed c pp in the star steamer and thorough rinsing in cold pound 1 part Of the copper compound of the water, in which case in the final rinsing, bath 2 dyestufi of the formula:

on HOOC-OHz-(|) o-om-ooon OH OCH:

is used a dull blue is obtained of very good fastness to light and washing.

grams per liter are added of a condensation product from dicyandiamidine and formaldehyde.

7 Example 8 there is produced a pure ruby red of very good 1 part of the copper compound of t dyestufi fastness to washing and excellent fastness to of the formula: llght.

N SOaNHa is mixed with 20 parts of urea and 4 parts of Example 9 IZZ-di-(fl hydroxyethylamino) ethane and 53 1 part of the dy tufi of the form l CIZOOH parts of hot water added together with 2 parts of is mixed with 4 parts of 1:2-cli-(fi-hydroxyethyl- 30 per cent. sodium hydroxide solution. After 30 amino) -ethane and 123 parts of water are added. bringing the solution to the boil it is stirred into The dyestuii is dissolved by bringing to the boil 120 parts of neutralized tragacanth thickening and the solution stirred into a mixture of 220 (60/1000). parts of neutralized tragacanth thickening By printing with this color on cotton or vis- (60/1000) and 40 parts of urea and finally 12 1 cose, drying, steaming for 10 minutes and thor- 35 parts added of a 10 per cent. solution of sodium oughly rinsing, a reddish brown print which is copper tartrate. fast to light and washing is obtained. By printing with this color on cotton or regen- By using instead of the above specified dyestufi erated cellulose, drying, steaming for 10 minutes 1 part of the copper compound of the dyestuff and thoroughly rinsing a brownish yellow print of the formula 40 is obtained which is fast to light and washing.

CHrC=N N=COH:

\ QC @Q I N -NHC O-NH- N 1103s N=No=( (13=CN=N 803B OH OH (I: coon OOH there is obtained according to the above direc- By employing instead of the above specified tions 2. pure yellow of excellent fastness to light dyestuff 1 part of the dyestuff of the formula OCH: OH OCH:

on I l l I 41003 on; Hols NH SOzH CH3 and superior fastness to washing. there is obtained according to the above direc- With 1 part of the copper compound of the tions a reddish blue of good fastness to washing dyestufi of the formula and light.

OH OH OH l CQ-NHQ comm-G Both prints are at least as strong and pure in a reddish brown results which is likewise of very shade as when the same dyestufis are printed good fastness to light and washing. according to known processes and after steam- In both cases there can be used instead of ing treated in an after--coppering bath. 1:2-di- (p-hydroxyethylamino) -ethane a, conden- A yellow print is obtained when the dyestufi 5 sation product which is obtained from 1 mol of of the formula 1:2-dich1orethane and either 2 mols of isopro- Boot 60011 is printed on cotton or regenerated cellulose acpanolamine or 2 mols of 2-amino-2-methylcording to the above directions. propane or 2 mols of 1:3-dihydroxy-2-amino-2 Example methylpropane.

1 part of the copper compound of the dyestuii mentioned in Example 9 (first paragraph) is mixed with 4 parts of 1:2-di-(fi-hydroxyethyl- Example 12 1 part of the copper compound of the dyestuif of the formula I 00011 NEz amino) -ethane, covered with 135 parts of water, is mixed with 4 parts of 1:2-di-(Q-hydroxythe solution brought to the boil and stirred into ethylamino) -ethane and covered with 135 parts a mixture of 220 parts of neutralized tragacanth of hot water. After bringing the solution to the thickening and parts of urea. boil it is stirred into a mixture of 220 parts of Printing and finishing are carried out as deneutralized tragacanth thickening (GO/1000) and scribed in Example 9 and a print is obtained of 40 parts of urea. equal value in all respects. 35 With this printing color there is obtained By using instead of the above specified dyestufi on cotton and regenerated cellulose, after the 1 part Of the copper compound of the dyestuff print has been dried, steamed for 10 minutes and set forth in Example 9 (second paragraph), a thoroughly rinsed, an excellently fixed blackreddish blue of equal value is obtained by the brown of good fastness to light. directions given. 49 What is claimed is:

Example 11 1. Process for printing with dyestuiis of subr stantive character which comprises applying to p Of the 1 1 compound of the y t fi the material to be printed a printing preparation of the formula which contains a metal complex compound,

is mixed with 4 parts of l:2-di-(;3-hydroxyethylwhich is difiicultly soluble per se, of. a substanamino) -ethane and the whole covered with 135 tive dyestuif, together with an organic nitrogen parts of hot water. After bringing to the boil base which corresponds to the formula the solution is stirred into 220 parts of neutra- R lized tragacanth thickening (/1000) and the L further addition made of 40 parts of urea. V N

With this printing color there is obtained on I R2 cotton or regenerated'cellulose after drying the 60 i hi R stands for a member of the group pl fi, Steaming 10 minutes and thoroughly consisting of a nitrogen atom, an alkyl group rm m n x ll n y fix d, tron Bordeaux. with at most three carbon atoms and a hydrox- By in instead of the above mentioned methylgroup, and R2 stands for a member of PD Compound 1 P Of the pp p n the group consisting of a hydrogen atom and a of the dyestufi of the formula methyl group, and n indicates a whole number COOH OH OH which is at most 4, and which contains as printing thickening a vegetable gum substantially free from reducing properties.

HOOC

2.. Process for printing with dyestuffs of substantive character which comprises applying to the material to be printed a printing preparation which contains a copper complex compound, which is difiicultly'soluble per se, of a substantive dyestuff, together with l:2edi-(fi-hydroxyethylamino) -ethane, and which contains as printing thickening a vegetable gum substantially free 12 the material to be printed a printing preparation which contains the copper-complex compound of the dyestufi of the formula CHr-C=N (313 $11 and 1:2-di-(B-hydroxyethylamino) -ethane and as a printing thickening a vegetable gum substantially free from reducing properties.

'7. Process for printing with dyestuffs of substantive character which comprises applying to the material to be printed a printing preparation which contains the copper-complex compound of the dyestufi of the formula COOH the material to be printed a printing preparation which contains the copper-complex compound of the dyestuff of the formula and 1 2-di-( B-hydroxyethylamino) -ethane and as a printing thickening a vegetable gum substantially free from reducing properties.

5. Process for printing with dyestuffs of substantive character which comprises. applying to the material to be printed a printing preparation which contains the copper-complex compound of the dyestuff of the formula COOH OH OOH:

and 1:2-difi-hydroxyethylamino) -ethane and as a printing thickening a vegetable gum-substantially free from reducing properties;

6. Process for printing with dyestufis of sub- OH OH and 1-:2-di-(B-hydroxyethylamino) ethane and as a printing thickening a vegetable gum substantially free from reducing properties.

8. A printing preparation which contains a metal complex compound, which is difficultly soluble per se, of a substantive dyestufi, together with an organic nitrogen base which corresponds to the formula R1 C H2n=(NH(:JCH2OH)? in which R1 stands for a member of the group consisting of a hydrogen atom, an alkyl group with at most three carbon atoms and a hydroxymethyl group, and R2 stands for a member of the group consisting of a hydrogen atom and a methyl group, and n indicates a whole numher which is at most 4, and which contains as printing thickening a vegetable gum substantially free from reducing properties.

9. A printing preparation which contains a copper complex compound, which is difficultly soluble per se, of a substantive dyestufitogether with 1 :2-di-( fi-hydroxyethylamino) -ethane, and

coon

(SOOH which contains as printing thickening a vegetable gum substantially free from reducing properties.

10. A printing preparation which contains stantive character which comprises applying to 75 such a copper complex compound of a substan- 13 tive dyestuff as, in the absence of a base, possesses at 80 C. a solubility of less than 0.5 gram per liter in 1 per cent. sodium carbonate solution, and also contains 1:2-di-(p3-hydroxyethylamino)-ethane and contains as printing thick- CHa-C=N ening a vegetable gum substantially free from reducing properties.

11. A printing preparation which contains the copper-complex compound of the dyestufi of the formula and 1 :2-di- (p-hydroxyethylamino) -ethane and. as a printing thickening a vegetable gum suband 1 2-cli- (p-hydroxyethylamino) -ethane and as a printing thickening a vegetable gum substantially free from reducing properties.

14. A printing preparation which contains the copper-complex compound of the dyestufi of the formula COOH stantially free from reducing properties.

12. A printing preparation which contains the OH OH HO: N=N

and 1:Z-di-(fi-hydroxyethylamino) -ethane and as a printing thickening a vegetable gum subcopper-complex compound of the dyestufi of the 40 stantially free from reducing properties.

formula COOK OH COOH References Cited in the file of this patent UNITED STATES PATENTS Date Apr. 18. 1933 Mendoza Mar. 31, 1936 Sept. 7, 1937 Sept. 23, 1941 FOREIGN PATENTS Country Date 468,362 Great Britain June 30. 1937 

1. PROCESS FOR PRINTING WITH DYESTUFFS OF SUBSTANTIVE CHARACTER WHICH COMPRISES APPLYING TO THE MATERIAL TO BE PRINTED A PRINTING PREPARATION WHICH CONTAINS A METAL COMPLEX COMPOUND WHICH IS DIFFICULTY SOLUBLE PER SE, OF A SUBSTANTIVE DYESTUFF, TOGETHER WITH AN ORGANIC NITROGEN BASE WHICH CORRESPONDS TO THE FORMULA 